KR20080074792A - Cleaning method and method for manufacturing electronic device - Google Patents

Abstract

A cleaning method and a method for manufacturing an electronic device are provided to improve the peeling/removing efficiency of a resist and contaminant by using peroxymonosurfate or peroxydisurfate. A concentrated sulfuric acid is electrolyzed to obtain an oxidizing solution(S1). The oxidizing solution is supplied to a nozzle(S2). The oxidizing solution is mixed with a hydrogen peroxide solution(H2O2), deionized water(H2O), or ozone water(O3+H2O) to prepare a cleaning solution(S3). The cleaning solution is sprayed to a rotational work piece through a movable nozzle(S4). The rotation work piece is cleaned by the cleaning solution sprayed from the movable nozzle(S5). After the cleaning process is completed, the rotational work piece is rinsed with a certain rinse solution(S6).

Description

CLEANING METHOD AND METHOD FOR MANUFACTURING ELECTRONIC DEVICE}

Cross Reference of Related Application

This application claims priority based on Japanese Patent Application No. 2007-031286, filed Feb. 9, 2007, and includes the entirety of the application on which the priority claim is based.

The present invention relates to a cleaning method and a manufacturing method of an electronic device, and more particularly, to a cleaning method using an oxidizing material produced by the electrolysis of sulfuric acid and a manufacturing method of the electronic device.

Typically, organic materials, metal impurities, particles, dry etch residues, and unwanted metals attached to liquid crystal display panel or plasma display panel (PDP) substrates and semiconductor wafers are used for SPM cleaning using a mixture of hot sulfuric acid and hydrogen peroxide. Or by a cleaning process based on a polymer cleaner consisting primarily of organic amines.

In contrast, Japanese Patent Laid-Open No. 2006-111943 discloses a cleaning method using persulfate ions generated by electrolysis of sulfuric acid solution.

With the recent trend toward miniaturization of devices, high capacity ion implantation processes are often needed to achieve high speed operation. However, a mask made of a resist or other organic material used in a high capacity ion implantation process has a problem that it is difficult to remove after the implantation process. Therefore, there is a need for a cleaning method having higher cleaning performance or organic material removal performance.

According to one aspect of the present invention, there is provided a cleaning method comprising electrolyzing sulfuric acid to produce an oxidizing solution, and cleaning the workpiece with the oxidizing solution heated by mixed heat.

According to another aspect of the invention, a method of manufacturing an electronic device comprising forming a workpiece, electrolyzing sulfuric acid to prepare an oxidizing solution, and cleaning the workpiece with the oxidized solution heated by mixed heat. This is provided.

The cleaning method according to the present invention can improve the stripping / removing efficiency of resists and contaminants, and obtain higher cleaning performance. The cleaning method of the present invention can be similarly applied to removing metal impurities, particles, dry etching residues, and the like, in addition to removing organic resists. In addition, the present invention can be used to manufacture electronic device related products (eg, semiconductor devices and display elements) to which the impurity cleaning method is applied.

Hereinafter, embodiments of the present invention will be described with reference to the drawings.

1 is a working flow diagram illustrating a cleaning method according to a first embodiment of the present invention.

More specifically, the cleaning method of this embodiment comprises the steps of electrolyzing concentrated sulfuric acid to obtain an oxidation solution (step S1); Supplying an oxidizing solution to the nozzle unit (step S2); Mixing a hydrogen peroxide solution (H ₂ 0 ₂ ), pure water (H ₂ 0) or ozone water (0 ₃ + H ₂ 0) into the oxidation solution (step S3); Discharging the cleaning liquid through the movable nozzle to the rotating workpiece to be cleaned (step S4); Cleaning the workpiece (step S5); And rinsing the workpiece (step S6).

2 is a schematic diagram illustrating a cleaning system capable of carrying out the cleaning method of the second embodiment.

In step S1, the oxidation solution is prepared by electrolyzing concentrated sulfuric acid in the sulfuric acid electrolysis unit 10. The sulfuric acid electrolysis unit 10 includes a positive electrode 32, a negative electrode 42, a diaphragm 20 provided between the positive electrode 32 and the negative electrode 42, and an anode defined between the positive electrode 32 and the diaphragm 20. Chamber 30 and cathode chamber 40 defined between cathode 42 and diaphragm 20.

Electrolyzed sulfuric acid, prepared by electrolysis of concentrated sulfuric acid, is an oxidizing solution containing an oxidizing substance. In step S2, the oxidizing solution is stored in the tank 28 through the conduit 73 with the open / close valve 73a, and the pump 81 is operated to supply the nozzle 61 through the conduit 74. do. The amount supplied to the nozzle 61 is controlled by the flow rate control by the open / close valve 74a and the flow rate control through the discharge passage 74c provided between the open / close valve 74a and the pump 81. In addition, the quantitative change of the oxidizing solution generated in the sulfuric acid electrolysis unit 10 can be buffered by storing the oxidizing solution in the tank 28. A heater can be provided in the tank 28, in which case the temperature of the oxidizing solution can be controlled. For example, higher cleaning performance can be obtained by heating the oxidizing solution in the tank 28 to a temperature of approximately 80 ° C.

By sulfuric acid electrolysis of sulfuric acid in the sulfuric acid electrolysis unit 10, an oxide material having high oxidizing ability, such as monosulfur peroxide (H ₂ S0 ₅ ) and disulfide peroxide (H ₂ S ₂ O ₈ ), is prepared as a reaction product. The oxidizing ability of these oxidizing materials is reduced by water. In particular, monosulfoxide, which is effective for stripping / removing organic matter, is decomposed by reaction with water. However, by providing 90% or more, more preferably 96% or more, concentrated sulfuric acid to the anode chamber 30 by way of example, the oxidizing material is present with a minimum amount of water. As a result, the quantitative and mass supply of monosulfate peroxide is possible. Thus, for example, the removal efficiency of the resist and contaminants can be improved, and the productivity can be increased.

The anode 32 of sulfuric acid electrolysis may be made of insoluble anode (DSA), platinum, lead dioxide or conductive diamond. The electrolyzed sulfuric acid produced by electrolysis in the sulfuric acid electrolysis section is used directly on workpieces to be cleaned, such as resist-coated silicon wafers where high cleanliness is required. Therefore, as the anode 32, it is preferable to use one of insoluble anodes (DSA), platinum, and conductive diamond having low elution of impurities. In particular, in order to achieve high oxygen overvoltages, it is more preferable to use conductive diamonds because of their high ability to produce oxide materials with high oxidative capacities such as mono-sulfur peroxide and disulfide peroxide.

On the other hand, the cathode 42 may be made of insoluble anode (DSA), platinum, carbon or conductive diamond.

As will be described in detail below, the cleaning process using electrolyzed sulfuric acid and the removal process of resist or other organic material vary greatly depending on the process temperature and it is preferred to carry out the process under heating. Therefore, in step S3, at least one of the hydrogen peroxide solution (H ₂ 0 ₂ ), pure water (H ₂ O) and ozone water (0 ₃ + H ₂ 0) is mixed into the electrolyzed sulfuric acid used as the oxidizing solution. That is, in this embodiment, the hydrogen peroxide solution, pure water or ozone water is mixed into the oxidizing solution before contacting the oxidizing solution with the workpiece W to be cleaned. The effect of dilution heat or reaction heat due to mixing increases the temperature of the electrolyzed sulfuric acid used as the oxidizing solution. This mixing is performed at the nozzle portion 12.

The supply of hydrogen peroxide solution, pure water or ozone water is carried out through the conduit 74d and the open / close valve 74b.

In step S4, the oxidizing solution mixed in step S3 is discharged to the workpiece W through the nozzle 61. The nozzle 61 may be moved to uniformly apply the oxidizing solution to the workpiece W. FIG. In addition, the workpiece W is mounted and rotated on the rotary table 62 provided in the cover 29. Due to the movement of the nozzle 61 and the rotation of the workpiece W, an oxidizing solution can be uniformly applied to the workpiece.

3 is a graph showing the temperature change according to the mixing ratio in the mixed solution of the hydrogen peroxide solution or the oxidizing solution mixed with the pure water in the nozzle unit 12.

Here, the cleaning experiment was performed by setting the temperature of the oxidizing solution before mixing to room temperature. This oxidizing solution was mixed with a hydrogen peroxide solution or pure water at the nozzle portion 12 of the system shown in FIG. 2 and dropped onto the wafer W. FIG. The temperature was measured by laser irradiation of the oxidizing solution dropped onto the wafer from the nozzle 61.

When mixed at a mixing ratio (volume ratio) of 1 part of pure water to 1 part of the oxidation solution, as shown in FIG. 3, the temperature was increased to approximately 115 ° C. by mixing heat (dilution heat). When the mixing ratio of pure water was increased to 2, 3 and 5, the temperature of the oxidizing solution gradually decreased to 95-80 ° C.

On the other hand, when the hydrogen peroxide solution (35 percent concentration) was mixed, the temperature increased to approximately 115 ° C. due to the heat of reaction (heat of reaction) when the mixing ratio (volume ratio) was 1. When the mixing ratio was increased to 2 and 3, the temperature was increased to 125 ° C and 130 ° C, and when the mixing ratio was increased to 5, the temperature was reduced to 110 ° C. As a result, it can be seen that the increase in temperature due to the mixing of pure water is larger than that in the case of mixing the hydrogen peroxide solution. As described in detail below, advantageous cleaning results were obtained under conditions in which the hydrogen peroxide solution was mixed at a mixing ratio 3.

Returning to FIG. 1, in step S5, the organic material or other contaminants on the workpiece W are stripped / removed by the oxidizing ability of the oxidizing solution. The contaminants that have been peeled / removed are in a solution or semi-solution state, are separated from the rotating work piece W by centrifugal force, and attached to the inner surface of the cover 29. The rotational speed of the turntable 62 affects the detachment of contaminants. Therefore, cleaning can be effectively performed by optimizing the rotational speed according to the contamination state.

In step S6, the rinse liquid is discharged to the surface of the work piece W through a nozzle (not shown) to rinse the work piece.

The oxidizing solution and contaminants discharged to the outside of the cover 29 are discharged to the outside of the system through the recovery tank 63, the discharge conduit 75 and the discharge valve 75a.

Next, in an embodiment in which a hydrogen peroxide solution or pure water is mixed with an oxidation solution obtained by electrolysis of concentrated sulfuric acid, the results of studying the cleaning effect using an evaluation sample are described.

Samples A and B were used as evaluation samples to be cleaned. Sample A was prepared by simply coating a silicon substrate to 3 microns thick using i-line resist. Sample B was prepared by doping boron at a capacity of 6 × 10 ¹⁴ / cm ² by ion implantation, after resist coating as described above. In connection with the processing method, the oxidized solution obtained by electrolysis of concentrated sulfuric acid was mixed with a hydrogen peroxide solution or pure water in the nozzle portion 12 of the system shown in FIG. 2 and dropped onto the wafer.

Measurements of whether the resist was successfully peeled off by cleaning can be made by surface observation with an optical microscope, evaluation with a particle counter, scanning electron microscope (SEM), and surface observation with an energy dispersive X-ray fluorescence spectrometer (EDX). Was done by.

First, the result of washing the evaluation sample A which mixed the hydrogen peroxide solution with the oxidizing solution and which was simply coated with a resist is described.

4 shows a table summarizing the results for Evaluation Sample A, which was simply coated with a resist.

This table shows the maximum temperature (° C) of the solution by the heat of mixing (heat of reaction) when the room temperature hydrogen peroxide solution is mixed with the room temperature oxidation solution. The time taken to peel off the applied resist at the temperature is shown in parentheses. When the mixing ratio (volume ratio) of the hydrogen peroxide solution to 1 part of the oxidation solution at room temperature was increased to 1, 2, 3, and 5, the maximum temperature was 115 ° C, 125 ° C, 130 ° C and It was 110 degreeC. On the other hand, when the mixing ratio (volume ratio) of the oxidizing solution to 1 volume of the hydrogen peroxide solution was increased to 1, 2, 3 and 5, the maximum temperature was changed to 115 ° C, 95 ° C, 80 ° C and 80 ° C. In both cases, the time to peel the resist was 5 seconds.

In other words, it can be seen that, for Sample A simply coated with a resist, high cleanability is achieved under any conditions. Also, high temperatures above 100 ° C. are obtained when the mixing ratio of oxidizing solution to hydrogen peroxide solution is 1: 1 to 1: 5, and high temperatures above 120 ° C. are obtained when the mixing ratio is 1: 2 to 1: 3. I can see your luggage.

5 is a table showing the results for Evaluation Sample B in which the applied resist was ion-implanted with the above-mentioned amount of boron. In general, resists are delaminated by ion implantation. As can be seen from FIG. 5, when pure water was mixed, the maximum temperature was 115 ° C. when the mixing ratio was 1: 1, and in this case, the time taken to peel the resist was 30 seconds. When the volume ratio of pure water was increased to 2, 3 and 5, as also shown in Fig. 3, the maximum temperature decreased continuously, in which case it was difficult to peel off the resist under any conditions.

On the other hand, when the hydrogen peroxide solution (35 percent concentration) is mixed at a volume ratio of 1, 2, 3, and 5 with respect to 1 volume of the oxidizing solution, as shown in FIG. 3, the maximum temperatures are 115 ° C., 125 ° C., 130 ° C., and 110. C, and the time taken to peel the resist was 30 seconds, 5 seconds, 1 second and 50 seconds. In other words, in all cases, the ion-implanted resist was successfully peeled off. In particular, when the maximum temperature was 125 ° C. or more, the peeling time was 5 seconds or less, which means that very strong detergency was achieved.

FIG. 6 shows a table summarizing the results of more detailed study on the case of adding the hydrogen peroxide solution.

Here, the results for the case of increasing the volume of the hydrogen peroxide solution to 1, 2, 3 and 5 with respect to 1 volume of the oxidizing solution are as described with reference to FIG. On the other hand, when the volume of the oxidizing solution with respect to 1 volume of mixed hydrogen peroxide solution was increased to 1, 2, 3 and 5, the maximum temperature was continuously decreased to 115 ° C, 95 ° C, 80 ° C and 80 ° C, and ion-transplanted. The time taken to peel off the resist was lengthened to 30 seconds, 65 seconds, 65 seconds and 65 seconds. That is, it can be seen that the washability continuously decreases as the temperature decreases.

Compared with the case where the pure water is mixed with reference to FIG. 5, the resist peeling is difficult when the pure water is mixed under the condition that the maximum temperature is 95 ° C. or 80 ° C., but the resist is peeled when the hydrogen peroxide is mixed. Was possible (FIG. 6). This is presumably due to the increase in temperature due to the mixing with the hydrogen peroxide solution, in addition, because sulfuric acid reacts with the hydrogen peroxide solution to increase the oxidizing substances with high oxidizing capacity, such as monoperoxide (H ₂ S0 ₅ ).

FIG. 7 is a graph summarizing the relationship between the temperature of an oxidized solution mixed with a hydrogen peroxide solution and the time taken for peeling with respect to Evaluation Sample B, in which the resist is ion-implanted with boron.

The time taken for the resist to peel off varies considerably with the temperature of the oxidizing solution. Above 95 ° C., the peel time was reduced and began to affect cleaning ability. When the maximum temperature reached 125 ° C., the time to peel off decreased to 5 seconds, which is almost the shortest time.

As can be seen from the above results, in order to improve the washing performance of the oxidized solution obtained by electrolyzing concentrated sulfuric acid, it is preferable to mix the hydrogen peroxide solution to raise the temperature to 95 ° C or higher. In addition, sufficiently high detergency can be achieved by mixing the hydrogen peroxide solution to increase the temperature to 125 ° C or higher.

Next, a second embodiment of the present invention will be described.

8 is an operational flowchart illustrating a cleaning process in the cleaning method according to the second embodiment of the present invention.

9 is a schematic diagram illustrating a cleaning system that may be used in the second embodiment.

In this embodiment, the mixing of the oxidizing solution and the hydrogen peroxide solution, pure water or ozone water is carried out on the workpiece to be cleaned.

Steps S1 and S2 are the same as in the first embodiment. However, in step S3, the hydrogen peroxide solution, pure water or ozone water is supplied to the nozzle unit 12 independently of the oxidizing solution generated and supplied by the sulfuric acid electrolysis unit 10.

Hydrogen peroxide solution, pure water or ozone water is supplied to the nozzle 61b through the conduit 74e and the open / close valve 74b.

In step S4a, the oxidizing solution is discharged onto the workpiece W through the nozzle 61a. In step S4b, at least one of the hydrogen peroxide solution, pure water and ozone water is discharged onto the workpiece W through the nozzle 61b. That is, in this embodiment, after the oxidizing solution comes into contact with the workpiece W, it is mixed with a hydrogen peroxide solution, pure water or ozone water. As in the first embodiment, the nozzles 61a and 61b can move to uniformly apply the oxidizing solution and the hydrogen peroxide solution, pure water or ozone water to the workpiece W, and the workpiece W is The mounted rotary table 62 rotates.

In step S5, the organic material or other contaminants on the workpiece W are stripped / removed by the oxidizing ability of the oxidizing solution. The contaminants peeled / removed are brought into a solution or semi-solution state, are separated from the rotating work piece W by centrifugal force, and adhered to the inner surface of the cover 29. The rotational speed of the turntable 62 affects the detachment of contaminants. Therefore, cleaning can be effectively performed by optimizing the rotational speed according to the contamination state.

10 is a graph showing the temperature change according to the mixing ratio in the mixed solution of the oxidizing solution and hydrogen peroxide solution or pure water mixed on the workpiece (W). Here, again, the temperature was measured using the radiation thermometer with respect to the oxidizing solution dripped from the nozzle 61a onto the workpiece | work W.

Before mixing, the temperatures of the oxidizing solution, pure water, and hydrogen peroxide solution were all set to room temperature. The temperature of the oxidizing solution increased with mixing with pure water or hydrogen peroxide solution. However, compared with the first embodiment where mixing is performed in the nozzle portion 12, the temperature increase of the oxidizing solution due to the mixing heat is smaller, and the temperature of the oxidizing solution is a result of the rotation of the workpiece W. May decrease. The temperature may also decrease inversely depending on the mixing ratio. This may be because the increase in temperature of the oxidizing solution due to the heat of mixing requires some time after the oxidizing solution is mixed with pure water or hydrogen peroxide solution.

Even in this embodiment, the cleaning experiments were conducted by sample A prepared by simply coating a silicon substrate with a thickness of 3 microns using an i-line resist, and after the resist coating, boron was implanted at an amount of 6 × 10 ¹⁴ / cm ² by ion implantation. This was done using Sample B prepared by doping at the dose.

FIG. 11 shows a table summarizing the results of cleaning Evaluation Sample A, which was simply coated with resist in a second embodiment.

Here, a table | surface shows the maximum temperature (degreeC) of the solution by the mixing heat (dilution heat) at the time of mixing pure water of room temperature with the oxidation solution of room temperature. The time taken to peel off the applied resist at the temperature is shown in parentheses. When the mixing ratio (volume ratio) of pure water to 1 part of the oxidation solution at room temperature was increased to 1, 2, 3 and 5, the maximum temperatures were 95 ° C, 87 ° C, 64 ° C and 60 ° C. On the other hand, when the mixing ratio (volume ratio) of the oxidizing solution to 1 volume of pure water was increased to 1, 2, 3 and 5, the maximum temperature was changed to 95 ° C, 96 ° C, 94 ° C and 75 ° C. In both cases, the time to peel the resist was 5 seconds.

In other words, even in this embodiment, it can be seen that, for Sample A simply coated with a resist, high cleaning performance is achieved under any conditions.

12 is a table showing the results for Evaluation Sample B in which the applied resist was ion-implanted with the above-mentioned amount of boron.

When pure water was mixed, the resist was successfully peeled off in 60 seconds when the mixing ratio was 1: 1. However, when the mixing ratio (volume ratio) of pure water was increased to 2, 3 and 5, it was difficult to peel off as the maximum temperature decreased.

On the other hand, when the hydrogen peroxide solution (35 percent concentration) was mixed at a volume ratio of 1, 2 and 3 with respect to 1 volume of the oxidizing solution, as shown in FIG. 10, the maximum temperatures were 95 ° C, 96 ° C and 94 ° C. The time to peel off was 30 seconds, 60 seconds and 90 seconds. When the mixing ratio of the hydrogen peroxide solution was 5, the maximum temperature was 75 ° C, and it was difficult to peel off the ion-implanted resist.

That is, even in this embodiment, when the temperature of the oxidizing solution after mixing is generally 95 ° C. or higher, it has been shown that high detergency can be achieved even when the ion-implanted resist is stripped off.

Next, a third embodiment of the present invention will be described.

13 is an operational flowchart illustrating a cleaning process in the cleaning method according to the third embodiment of the present invention.

14 is a schematic diagram illustrating a cleaning system that may be used in the third embodiment.

In this embodiment, the hydrogen peroxide solution, pure water or ozone water is mixed into an oxidizing solution obtained by the electrolysis of concentrated sulfuric acid, and further, monohydric peroxide or a salt thereof, or disulfide peroxide or a salt thereof is further added to the nozzle portion 12. Mix in.

The process of steps S1 to S2 is the same as in the first embodiment. In step S3, the hydrogen peroxide solution, pure water or ozone water is supplied to the nozzle portion 12 through the conduit 74d and the open / close valve 74b.

In step S7, monosulfuric acid peroxide or a salt thereof, or disperoxide peroxide or a salt thereof, or both are further supplied to the nozzle portion 12 through a conduit 74f. The process of S4 and subsequent processes are the same as in the first embodiment.

For example, if the hydrogen peroxide solution is mixed in step S3 and the ammonium persulfate solution is mixed in step S7, higher detergency is achieved by increasing the oxidation solution temperature due to the heat of reaction and the oxidative properties of ammonium persulfate. That is, according to this embodiment, a cleaning liquid having a strong oxidation capacity can be prepared by mixing a disulfide peroxide, a salt thereof, or a similar material having a strong oxidation capacity in addition to the oxidized material produced by the electrolysis of concentrated sulfuric acid. As a result, highly ion-implanted resist can be removed very quickly, for example.

15 is a working flowchart illustrating a method of manufacturing an electronic device according to an embodiment of the present invention.

First, a work piece is formed (step S10). For example, the glass substrate for flat panel display manufacture, such as a semiconductor wafer for semiconductor element manufacture, or a liquid crystal display, can be formed as a work piece. The workpiece can include a layer of resist that is removed on its surface by the following cleaning step.

 Secondly, sulfuric acid is electrolyzed to prepare an oxidation solution (step S20). Specifically, a process as described in connection with step S1 shown in Figs. 1, 3 and 13 can be used in the present manufacturing process.

Next, the workpiece is cleaned (step S30). Specifically, as shown in Fig. 1, 8 or 13, step S2 to step S5 can be used for the present cleaning process. The resist layer formed on the surface of the workpiece can be removed by a cleaning process (step S30). Thereafter, the workpiece can be rinsed.

Embodiments of the invention have been described in connection with the examples. However, the present invention is not limited to the above embodiment. For example, the method of mixing the oxidizing solution with a hydrogen peroxide solution, monoperoxide, or the like may vary. Specifically, in the third embodiment, the step of mixing the oxidizing solution with monosulfuric acid peroxide or the like may be performed on the workpiece W, not the nozzle portion 12.

In addition to removing organic resists, the present invention can also be similarly applied to removing metal impurities, particles and dry etch residues.

In addition, the present invention can be used to manufacture electronic device related products (eg, semiconductor devices and display elements) to which the impurity cleaning method is applied.

1 is a working flow diagram illustrating a cleaning method according to a first embodiment of the present invention.

2 is a schematic diagram illustrating a cleaning system capable of carrying out the cleaning method of the first embodiment.

3 is a graph showing the temperature change according to the mixing ratio in the mixed solution of the hydrogen peroxide solution or the oxidizing solution mixed with the pure water in the nozzle unit 12.

4 shows a table summarizing the results for Evaluation Sample A, which was simply coated with a resist.

FIG. 5 is a table showing the results for Evaluation Sample B in which the applied resist was ion-implanted with a certain amount of boron.

FIG. 6 shows a table summarizing the results of more detailed study on the case of adding hydrogen peroxide solution.

FIG. 7 is a graph summarizing the relationship between the temperature of an oxidized solution mixed with a hydrogen peroxide solution and the time taken for peeling with respect to Evaluation Sample B, in which the resist is ion-implanted with boron.

8 is an operational flowchart illustrating a cleaning process in the cleaning method according to the second embodiment of the present invention.

9 is a schematic diagram illustrating a cleaning system that may be used in the second embodiment.

10 is a graph showing the temperature change according to the mixing ratio in the mixed solution of the oxidizing solution and hydrogen peroxide solution or pure water mixed on the workpiece (W).

FIG. 11 shows a table summarizing the results of cleaning Evaluation Sample A, which was simply coated with resist in a second embodiment.

12 is a table showing the results for Evaluation Sample B in which the applied resist was ion-implanted with a certain amount of boron.

13 is an operational flowchart illustrating a cleaning process in the cleaning method according to the third embodiment of the present invention.

14 is a schematic diagram illustrating a cleaning system that may be used in the third embodiment.

15 is a working flowchart illustrating a method of manufacturing an electronic device according to an embodiment of the present invention.

Claims (21)

Electrolyzing sulfuric acid to prepare an oxidizing solution, and Cleaning the workpiece with the oxidizing solution heated by mixed heat. The method of claim 1, wherein the oxidizing solution comprises at least one of mono-sulfur peroxide and disulfide peroxide. The cleaning method according to claim 1, wherein the mixed heat is generated by mixing at least one of pure water, hydrogen peroxide solution, and ozone water with the oxidizing solution. 4. The method of claim 3, wherein said mixing step is performed before contacting the oxidizing solution with the workpiece. The cleaning method according to claim 4, wherein the mixing step is performed at a nozzle which discharges the oxidizing solution to the work piece. 4. The method of claim 3, wherein said mixing step is performed after contacting the oxidizing solution with the workpiece. The cleaning method according to claim 1, wherein at least one member selected from the group consisting of monosulfur peroxide, a salt of monosulfur peroxide, a disulfide peroxide, and a salt of disulfide peroxide is added to the oxidizing solution. 4. The cleaning method according to claim 3, wherein at least one member selected from the group consisting of monosulfur peroxide, a salt of monosulfur peroxide, a disulfide peroxide, and a salt of disulfide peroxide is added to the oxidation solution. The cleaning method according to claim 1, wherein the anode of the electrolysis section is made of one selected from the group consisting of an insoluble anode, platinum, lead dioxide or conductive diamond. The cleaning method according to claim 1, wherein the anode of the electrolysis section is made of conductive diamond. The cleaning method according to claim 1, wherein the cathode of the electrolysis section is made from one selected from the group consisting of insoluble anode, platinum, carbon and conductive diamond. The method of claim 3, wherein the oxidizing solution is heated before the mixing step. The cleaning method according to claim 1, wherein the oxidizing solution is brought into contact with the work piece while moving the nozzle releasing the oxidizing solution. The cleaning method according to claim 1, wherein the oxidizing solution is brought into contact with the workpiece while rotating the table on which the workpiece is mounted. The method of claim 3, wherein the hydrogen peroxide solution is mixed at a volume ratio of 1 to 5 with respect to 1 volume of the oxidizing solution. The method of claim 1 wherein the concentration of sulfuric acid is at least 90 weight percent. Forming a workpiece; Electrolyzing sulfuric acid to prepare an oxidation solution; And Cleaning the workpiece with the oxidizing solution heated by mixed heat. The method of claim 17, wherein the workpiece comprises an ion-implanted resist. The method of manufacturing an electronic device according to claim 18, wherein the resist is peeled off by heating an oxidizing solution to 95 ° C. or higher. The method of claim 18, wherein the oxidizing solution is heated to 125 ° C. or higher. 19. The method of claim 18, wherein the resist is stripped by an oxidizing solution comprising 1 to 5 volume ratios of hydrogen peroxide solution relative to 1 volume of the oxidizing solution.

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